The present invention relates to three-dimensional (3-D) modeling in general and to methods and compositions for use in 3-D printing of complex structures in particular.
3-D printing, which works by building parts in layers, is a process used for the building up of 3-D models. 3-D printing is relatively speedy and flexible, allowing for the production of prototype parts and tooling directly from a CAD model, for example.
Using 3-D printing enables the manufacturer to obtain a full 3-D model of any proposed product before tooling, thereby possibly substantially reducing the cost of tooling and leading to a better synchronization between design and manufacturing. A lower product cost and improved product quality can also be obtained.
Various systems have been developed for computerized 3-D printing. In U.S. Pat. No. 6,259,962 to the Assignees of the present application, and incorporated herein by reference, there is described an apparatus and a method for 3-D model printing. U.S. Pat. No. 6,259,962 describes apparatus including a printing head having a plurality of nozzles, a dispenser connected to the printing head for selectively dispensing interface material in layers, and curing means for optionally curing each of the layers deposited. The depth of each deposited layer is controllable by selectively adjusting the output from each of the plurality of nozzles.
In U.S. patent application Ser. No. 09/412,618 to the Assignees of the present invention, and incorporated herein by reference, there is described an apparatus and a method for 3-D model printing. U.S. patent application Ser. No. 09/412,618 describes a system and a method for printing complex 3-D models by using interface materials having different hardness or elasticity and mixing the interface material from each of the printing heads to control the hardness of the material forming the 3-D model. The construction layers of the model are formed from interface material having a different (harder) modulus of elasticity than the material used to form the release (and support) layers, thereby allowing for the forming of complex shapes.
Radiation curable inks are disclosed in U.S. Pat. Nos. 4,303,924, 5,889,084, and 5,270,368. U.S. Pat. No. 4,303,924 discloses radiation curable compositions for jet-drop printing containing multifunctional ethylenically unsaturated material, monofunctional ethylenically unsaturated material, a reactive synergist, a dye colorant and an oil soluble salt. U.S. Pat. No. 5,889,084 discloses a radiation curable ink composition for ink-jet printing which comprises a cationically photoreactive epoxy or vinyl ether monomer or oligomer, a cationic photo-initiator and a coloring agent. U.S. Pat. No. 5,270,368 discloses a UV curable ink composition for ink-jet printing comprising a resin formulation having at least two acrylate components, a photo-initiator and an organic carrier.
The ink compositions disclosed in these references are formulated for use in ink-jet printing. Compositions for ink-jet printing are formulated differently from compositions for building 3-D models, and thus have different properties. For example, high viscosity at room temperature is a desirable property for 3-D objects, and thus compositions for building 3-D models are designed to have a high viscosity at room temperature. In contrast, compositions for inkjet printing are designed to have low viscosity at room temperature in order to function well in the printing process. None of the above-mentioned references disclose compositions that are especially formulated for 3-D printing.
Radiation curable inks for 3-D objects are disclosed in U.S. Pat. No. 5,705,316. U.S. Pat. No. 5,705,316 discloses compounds having at least one vinyl ether group, which also contain in the molecule at least one other functional group such as an epoxy or an acrylate group; compositions comprising these compounds; and methods of producing 3-D objects using these compositions. The compounds of U.S. Pat. No. 5,705,316 are complex molecules that are not readily available and thus need to be especially synthesized, which incurs additional time and costs.
None of the above mentioned references provides simple, easily obtainable curable compositions that are suitable for use in 3-D printing. In addition, the above mentioned references do not provide compositions for use in supporting and/or releasing a 3-D model during construction. Finally, the above mentioned references do not provide methods for 3-D printing, by using interface materials having different hardness or elasticity and by mixing the interface materials to control the hardness of the material forming the 3-D model.
Thus, there is a need for simple, easily obtainable curable compositions, that are specially formulated to construct a 3-D model. There is further a need for simple, easily obtainable curable compositions, that are specially formulated to provide support to a 3-D, by forming support/and or release layers around a 3-D object during construction. Lastly, there is a need for methods of constructing a 3-D by using the above mentioned compositions.
The present invention relates to compositions for use in the manufacture of 3-D objects. The present invention further relates to compositions for use as a support and/or release material in the manufacture of said 3-D objects. The present invention further relates to method for the preparation of a 3-D object by 3-D printing, and to a 3-D object obtained by said method.
There is thus provided, in accordance with an embodiment of the present invention, a composition for use in the manufacture of 3-D objects by a method of selective dispensing. The composition comprises
at least one reactive component;
at least one photo-initiator;
at least one surface-active agent; and
at least one stabilizer.
The composition has a first viscosity above 50 cps at room temperature, and a second viscosity compatible with ink-jet printers at a second temperature, wherein said second temperature is higher than room temperature.
In accordance with an embodiment of the present invention, the reactive component is an acrylic component, a molecule having one or more epoxy substituents, a molecule having one or more vinyl ether substituents, vinylcaprolactam, vinylpyrolidone, or any combination thereof.
Furthermore, in accordance with an embodiment of the present invention, the reactive component is an acrylic component. The acrylic component is an acrylic monomer, an acrylic oligomer, an acrylic crosslinker, or any combination thereof.
Furthermore, in accordance with an embodiment of the present invention, the reactive component comprises an acrylic component and in addition a molecule having one or more epoxy substitutents, a molecule having one or more vinyl ether substituents, vinylcaprolactam, vinylpyrolidone, or any combination thereof.
Furthermore, in accordance with an embodiment of the present invention, the reactive component comprises an acrylic component and vinylcaprolactam.
Furthermore, in accordance with an embodiment of the present invention, the reactive component comprises a molecule having one or more vinyl ether substitutents.
Furthermore, in accordance with an embodiment of the present invention, the reactive component comprises a molecule having one or more epoxy substituents.
Furthermore, in accordance with an embodiment of the present invention, the reactive component comprises a molecule having one or more vinyl ether substituents, and a molecule having one or more epoxy substitutents.
Furthermore, in accordance with an embodiment of the present invention, the photo-initiator is a free radical photo-initiator, a cationic photo-initiator, or any combination thereof.
Furthermore, in accordance with an embodiment of the present invention, the composition further comprises at least one pigment and at least one dispersant. The pigment is a white pigment, an organic pigment, an inorganic pigment, a metal pigment or a combination thereof. In one embodiment, the composition further comprises a dye.
Furthermore, in accordance with an embodiment of the present invention, the first viscosity of the composition is greater than 80 cps. In one embodiment, the first viscosity is between 80 and 300 cps. In another embodiment, the first viscosity is around 300 cps.
Furthermore, in accordance with an embodiment of the present invention, the second viscosity of the composition is lower than 20 cps at a second temperature, which is greater than 60 C. Preferably, the second viscosity is between 8 and 15 cps at the second temperature, which is greater than 60 C. In one embodiment, the second viscosity is about 11 cps at a temperature around 85 C.
In addition, in accordance with another embodiment of the present invention, there is thus provided a composition for use as a support and/or release material in the manufacture of 3-D objects by a method of selective dispensing. The composition comprises
at least one non-reactive and low toxicity compound
at least one surface-active agent; and
at least one stabilizer.
The composition has a first viscosity above 50 cps at room temperature, and a second viscosity compatible with ink-jet printers at a second temperature, wherein said second temperature is higher than room temperature.
In accordance with an embodiment of the present invention, the composition further comprises at least one reactive component and at least one photo-initiator. The reactive component is at least one of an acrylic component, a molecule having one or more vinyl ether substituents, or the reactive component is a water miscible component that is, after curing, capable of swelling upon exposure to water or to an alkaline or acidic water solution.
Furthermore, in accordance with an embodiment of the present invention the reactive component is an acrylic component. The acrylic component is an acrylic oligomer, an acrylic monomer, or a combination thereof.
Furthermore, in accordance with an embodiment of the present invention, the reactive component comprises at least one water miscible component that is, after curing, capable of swelling upon exposure to water or to an alkaline or acidic water solution. The water miscible component is preferably an acrylated urethane oligomer derivative of polyethylene glycol, a partially acrylated polyol oligomer, an acrylated oligomer having hydrophillic substituents, or any combination thereof. The hydrophilic substituents are preferably acidic substituents, amino substituents, hydroxy substituents, or any combination thereof.
Furthermore, in accordance with an embodiment of the present invention, the reactive component comprises a molecule having one or more vinyl ether substituents.
Furthermore, in accordance with an embodiment of the present invention, the non-reactive component is polyethylene glycol, methoxy polyethylene glycol, glycerol, ethoxylated polyol, or propylene glycol.
Furthermore, in accordance with an embodiment of the present invention, the photo-initiator is a free radical photo-initiator, a cationic photo-initiator, or a combination thereof.
Furthermore, in accordance with an embodiment of the present invention, the first viscosity of the composition is greater than 80 cps. In one embodiment, the first viscosity is between 80 and 300 cps. In another embodiment, the first viscosity is around 200 cps.
Furthermore, in accordance with an embodiment of the present invention, the second viscosity of the composition is lower than 20 cps at a second temperature, which is greater than 60 C. Preferably, the second viscosity is between 8 and 15 cps at the second temperature, which is greater than 60 C. In one embodiment, the second viscosity is about 11 cps at a temperature around 85 C.
In addition, there is thus provided, in accordance with an embodiment of the present invention, a method for preparation of a 3-D object by 3-D printing. The method comprises
dispensing a first interface material from a printing head, the first interface material comprising
at least one reactive component;
at least one photo-initiator;
at least one surface-active agent; and
at least one stabilizer;
dispensing a second interface material from said printing head, the second interface material comprising
at least one non-reactive and low toxicity compound;
at least one surface-active agent; and
at least one stabilizer;
combining the first interface material and the second interface material in pre-determined proportions to produce construction layers for forming the 3-D object.
Furthermore, in accordance with an embodiment of the present invention, the reactive component of the first interface material is an acrylic component, a molecule having one or more epoxy substituents, a molecule having one or more vinyl ether substituents, vinylpyrolidone, vinylcaprolactam, or any combination thereof.
Furthermore, in accordance with an embodiment of the present invention, the reactive component of the first interface material comprises an acrylic component. The acrylic component is an acrylic monomer, an acrylic oligomer, an acrylic crosslinker, or any combination thereof.
Furthermore, in accordance with an embodiment of the present invention, the reactive component of the first interface material comprises an acrylic component and in addition a molecule having one or more epoxy substituents, a molecule having one or more vinyl ether substituents, vinylcaprolactam, vinylpyrolidone, or any combination thereof.
Furthermore, in accordance with an embodiment of the present invention, the reactive component of the first interface material comprises an acrylic component and vinylcaprolactam.
Furthermore, in accordance with an embodiment of the present invention, the reactive component of the first interface material is a molecule having one or more vinyl ether substituents.
Furthermore, in accordance with an embodiment of the present invention, the reactive component of the first interface material is a molecule having one or more epoxy substituents.
Furthermore, in accordance with an embodiment of the present invention, the reactive component of the first interface material comprises a molecule having one or more epoxy substituents, and a molecule having one or more vinyl ether substituents.
Furthermore, in accordance with an embodiment of the present invention, the first interface material further comprises at least one pigment and at least one dispersant. The pigment is a white pigment, an organic pigment, an inorganic pigment, a metal pigment or a combination thereof. In one embodiment, the first interface material further comprises a dye.
Furthermore, in accordance with an embodiment of the present invention, the method further comprises the step of curing said first interface material.
Furthermore, in accordance with an embodiment of the present invention, the second interface material further comprises at least one reactive component and at least one photo-initiator. The reactive component is at least one of an acrylic component, a molecule having one or more vinyl ether substituents, or the reactive component is a water miscible component that is, after curing, capable of swelling upon exposure to water or to an alkaline or acidic water solution.
Furthermore, in accordance with an embodiment of the present invention the reactive component is an acrylic component. The acrylic component is an acrylic oligomer, an acrylic monomer, or a combination thereof.
Furthermore, in accordance with an embodiment of the present invention, the reactive component comprises at least one water miscible component that is, after curing, capable of swelling upon exposure to water or to an alkaline or acidic water solution. The water miscible component is preferably an acrylated urethane oligomer derivative of polyethylene glycol, a partially acrylated polyol oligomer, an acrylated oligomer having hydrophillic substituents, or any combination thereof. The hydrophilic substituents are preferably acidic substituents, amino substituents, hydroxy substituents, or any combination thereof.
Furthermore, in accordance with an embodiment of the present invention, the reactive component of the second interface material comprises a molecule having one or more vinyl ether substituents.
Furthermore, in accordance with an embodiment of the present invention, the non-reactive component is polyethylene glycol, methoxy polyethylene glycol, glycerol, ethoxylated polyol, or propylene glycol.
Furthermore, in accordance with an embodiment of the present invention, the photo-initiator of the first interface material and optionally of the second interface material is a free radical photo-initiator, a cationic photo-initiator or any combination thereof.
Furthermore, in accordance with an embodiment of the present invention, the method further comprises the step of curing the second interface material.
Furthermore, in accordance with an embodiment of the present invention, the first interface material and the second interface material have a different modulus of elasticity and a different strength. In one embodiment, the first interface material has a higher modulus of elasticity and a higher strength than the second interface material.
Furthermore, in accordance with an embodiment of the present invention, the method further comprises the step of forming a multiplicity of support layers for supporting the object. In one embodiment, the support layers are formed by combining the first interface material and the second interface material in pre-determined proportions. In one embodiment, the support layers have the same modulus of elasticity and the same strength as the construction layers. In another embodiment, the support layers have a lower modulus of elasticity and a lower strength than the construction layers.
Furthermore, in accordance with an embodiment of the present invention, the method further comprises the step of combining the first interface material and the second interface material in pre-determined proportions to form a multiplicity of release layers for releasing the support layers from the object. In one embodiment, the release layers have a lower modulus of elasticity and a lower strength than the construction layers and the support layers.
Furthermore, in accordance with an embodiment of the present invention, the first interface material and said second interface material each have a first viscosity at room temperature, and a second viscosity compatible with ink-jet printers at a second temperature, which may be the same or different, wherein said second temperature is higher than room temperature.
In addition, there is thus provided, in accordance with another embodiment of the present invention, a 3-D object comprised of a core consisting of a multiplicity of construction layers. The construction layers are prepared by combining pre-determined proportions of the first interface material and the second interface material, described hereinabove.
Furthermore, in accordance with an embodiment of the present invention, the object further comprises a multiplicity of support layers for supporting the core. In one embodiment, the support layers are prepared by combining pre-determined proportions of the first interface material and a second interface material. In one embodiment, the support layers have the same modulus of elasticity and the same strength as the construction layers. In another embodiment, the support layers have a lower modulus of elasticity and a lower strength than the construction layers.
Furthermore, in accordance with a preferred embodiment of the present invention, the object further comprises a multiplicity of release layers for releasing the support layers from the core. In one embodiment, the release layers are positioned between the support layers and the construction layers. The release layers are prepared by combining pre-determined proportions of the first interface material and a second interface material. In one embodiment, the release layers have a lower modulus of elasticity and a lower strength than the construction layers and the support layers.